CN104650116A - Organic compound and application thereof in organic electroluminescence devices - Google Patents

Organic compound and application thereof in organic electroluminescence devices Download PDF

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CN104650116A
CN104650116A CN201310730759.0A CN201310730759A CN104650116A CN 104650116 A CN104650116 A CN 104650116A CN 201310730759 A CN201310730759 A CN 201310730759A CN 104650116 A CN104650116 A CN 104650116A
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naphthyl
compound
phenyl
boric acid
pyrimidine
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CN104650116B (en
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李银奎
汤金明
范洪涛
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Beijing Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

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Abstract

The invention relates to an organic compound as shown in a formula (I). In the formula, one of A and B is N, and the other one is a CH group or a CH group of which H is substituted by one of alkyl of C1-12, aryl of C6-30, heterocyclic aryl of C6-30, -CF3 and -SCH3; n is 1 or 2; Ar is selected from anthryl, anthrylene, anthracenediyl or anthracenediylene which can be substituted by one of phenyl, biphenyl, naphthyl and naphthyl phenyl; L is a bridging ligand, and is selected from single bond, arylidene, penta-heterocyclic or hexa-heterocyclic aryl, oxygen atoms, nitrogen atoms or sulfur atoms; Ar1 and Ar2 are independently selected from H, phenyl, naphthyl and biphenyl which can be substituted by one of alkyl of C1-12, -CF3, -SCH3, phenyl, biphenyl and naphthyl. The invention further provides application of the compound in organic electroluminescence devices, in particular electronic transmission materials of an OLED.

Description

A kind of organic compound and the application in organic electroluminescence device thereof
Technical field
The present invention relates to a kind of novel organic compound, and the application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent material and device, through years of researches and development, have reached practical level, various material, such as hole material, electronic material, luminescent material, and display device technology of preparing has achieved considerable progress.Similarly, all types of electron transport materials that transmittability is stronger, stability is higher, have report in article and patent.In general, electron transport material is all the plane aromatics with large conjugated structure, and they mostly have and connect nucleophobic ability preferably, effectively can transmit electronics again under certain forward bias simultaneously.Used electron transport material mainly contains oxine aluminium compounds, furodiazole compound, quinoxaline compound, the polymkeric substance of nitrile group-containing, (Chem.Mater.2004,16,4556-4573 such as other nitrogen-containing heterocycle compound, J Mater.Chem.2005,15,94-106).Condensed-nuclei aromatics electron transport material (the application publication number CN101891673A that current newer report has phenylpyridyl to replace, Shen Qing Publication day 2010,11,24), condensed-nuclei aromatics electron transport material (application number 200910234761.2, the applying date 2009,11 that benzoglyoxaline group replaces, 13), etc.
Therefore, based on existing research, the electron transport material of exploitation stability and high efficiency further, thus reduced bright voltage, improve device efficiency, there is very important actual application value.
Summary of the invention
The object of the present invention is to provide a class novel organic compound, this compounds may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field, concrete, this compounds is in organic electroluminescence device, as electron transport material, and then it is low to obtain driving voltage, the organic electroluminescence device that current efficiency is high, the transformation period is longer.
For this reason, the technical scheme that the present invention takes is:
A kind of organic compound, has the structure as shown in formula I:
Wherein:
A and B one of them be N, another be H in CH group or CH group by the alkyl of C1-12, carbonatoms be the aryl of 6-30, carbonatoms is the heterocyclic aryl ,-CF of 6-30 3,-SCH 3in a kind of group of replacement;
N value 1 or 2;
Ar is selected from anthryl, phenyl, xenyl, naphthyl, naphthylphenyl be the anthryl that replaces of a kind of group wherein, anthrylene, phenyl, xenyl, naphthyl, naphthylphenyl be the anthrylene that replaces of a kind of group wherein, dianthranide base, the dianthranide base of phenyl, xenyl, naphthyl, naphthylphenyl, sub-dianthranide base, phenyl, xenyl, naphthyl, naphthylphenyl wherein the sub-dianthranide base that replaces of a kind of group one of them;
L is bridge linkage group, be selected from singly-bound, three substituted heterocycle aryl, Sauerstoffatom, nitrogen-atoms or sulphur atom that sub-heterocyclic aryl that trisubstituted aryl that arylidene that carbonatoms is 6-30, carbonatoms are 6-30, carbonatoms are 6-30, carbonatoms are 6-30 one of them;
Ar 1and Ar 2separately be selected from H, phenyl, C 1-12alkyl ,-CF 3,-SCH 3, phenyl, xenyl, the naphthyl wherein phenyl that replaces of a kind of group, naphthyl, C 1-12alkyl ,-CF 3,-SCH 3, phenyl, xenyl, the naphthyl wherein naphthyl that replaces of a kind of group, five yuan or hexa-member heterocycle aromatic group, the aliphatic alkyl of 1-12 carbon atom one of them.
Further, described compound has formula II or the structure described in (III):
Further, described bridge linkage group L is selected from one of them of singly-bound, phenylene, biphenylene, naphthylidene, pyridylidene, Sauerstoffatom, nitrogen-atoms or sulphur atom.
In order to be illustrated more clearly in content of the present invention, lower mask body describes the organic compound that the present invention relates to and selects preferred structure to be:
The invention provides a kind of organic compound that can be applicable in organic electroluminescence device.
Organic compound of the present invention has higher electron transfer capabilities, in organic electroluminescence device, be used as electron transport material.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer,
The electron transport material of described electron transfer layer is described organic compound.
Further, the electron transport material in organic electroluminescence device can also by the compound of the application and other compounds with the use of, jointly as electron transport material.
Compared with prior art, tool of the present invention has the following advantages:
(1) based on contriver oneself research and design and synthesize, test a class for the dianthranide derivative for electron transport material in OLED, propose using anthryl or dianthranide base as parent nucleus, the imidazo [1 of electron deficiency, 2-a] pyrimidine group or imidazo [1,2-a] pyrazine group as electron deficiency substituting group, form a class new compound.Because anthracene has larger conjugated structure, and have the plane regularity of its uniqueness, be combined after forming this kind of new compound with electron deficiency substituting group, anthracene still keeps its plane regularity feature, highest occupied molecular orbital(HOMO) (HOMO) and lowest unoccupied molecular orbital (LUMO) are mainly distributed on anthracene nucleus, and large and regular planar conjugate is conducive to the transmission of electronics in molecular orbital(MO).9, no matter whether 9 '-dianthranide group has substituting group, its all orthogonal thereto state of two anthracene nucleus, two anthracene nucleus all maintain its respective plane regularity feature, after being combined with electron deficiency substituting group and forming this kind of material, HOMO and LUMO is equally mainly distributed on two orthogonal anthracene nucleus, and large and regular planar conjugate system is conducive to the injection of electronics in molecular orbital(MO) and transmission.
(2) preparation is simple for the compounds of this invention, and these compounds have good thermostability, high electronic mobility, the electroluminescent device electroluminescence efficiency made of this material significantly improves, the life-span of device also improves greatly simultaneously, can be used as electron transport material in organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is the highest occupied molecular orbital(HOMO) (HOMO, energy level-5.357ev use Gaussian03/6-31 method) of compound 2 in the embodiment of the present invention;
Fig. 2 is the lowest unoccupied molecular orbital (LUMO, energy level-1.903ev use Gaussian03/6-31 method) of compound 2 in the embodiment of the present invention;
Fig. 3 is the highest occupied molecular orbital(HOMO) (HOMO, energy level-5.557ev use Gaussian03/6-31 method) of embodiment of the present invention compound 27;
Fig. 4 is the lowest unoccupied molecular orbital (LUMO, energy level-2.370ev use Gaussian03/6-31 method) of embodiment of the present invention compound 27.
Embodiment
Various imidazos [1 used in the present invention, 2-a] pyrimidine halo derivatives and imidazo [1, 2-A] pyrazine halo derivatives, such as, 5, 7-dichloro-imidazole also [1, 2-a] pyrimidine, 6-bromine imidazo [1, 2-a] pyrimidine, 3-bromine imidazo [1, 2-a] pyrimidine, the chloro-5-of 7-(methylthio group) imidazo [1, 2-c] pyrimidine, 3-bromo-6-chlorine imidazo [1, 2-a] pyrimidine, 5, 7-dichloro-imidazole also [1, 2-A] pyrimidine, 2-(3-bromophenyl) imidazoles [1, 2-a] and pyrimidine, the chloro-2-p-tolylimidazol [1 of 6-, 2-a] and pyrimidine, 2-(4-bromophenyl)-imidazo [1, 2-a]-7-methylpyrimidine, 2-(3-bromophenyl)-imidazo [1, 2-a] pyrimidine, 2-(3-bromophenyl)-imidazo [1, 2-a]-7-methylpyrimidine, 2-(4-bromophenyl)-imidazo [1, 2-a] pyrimidine, the chloro-2-Vermox of 6-also [1, 2-a] pyrimidine, 2-(4-bromophenyl)-7-Methylimidazole [1, 2-a] and pyrimidine, the bromo-7-of 3-(trifluoromethyl) imidazo [1, 2-a] pyrimidine, 6-bromine imidazo [1, 2-A] pyrazine, 3-bromo-8-chlorine imidazo [1, 2-A] pyrazine, 6, the bromo-imidazoles [1 of 8-bis-, 2-A] pyrazine, the chloro-imidazo [1 of 5-, 2-A] pyrazine, 8-chlorine imidazo [1, 2-a] pyrazine, 3-bromine imidazo [1, 2-a] pyrazine, 2-bromine imidazo [1, 2-a] pyrazine etc., commercially available all at home, the chemical raw materials such as various aryl boric acid and Knit-the-brows alcohol ester thereof, can conveniently buy in Chemicals market at home, some special aryl boric acid derivatives and all available common organic procedures synthesis of intermediate.
Embodiment 1
The present embodiment prepares compound 1, and its structure is as follows:
This compou nd synthesis carries out in two steps, the first step,
In one 500 milliliters of there-necked flasks, join magnetic agitation, after nitrogen replacement, add 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine 9.24g(molecular weight 231,0.040mol by above-mentioned amount successively), THF230ml.Butyllithium 20ml(concentration 2.5M, 0.05mol is dripped under-78 ° of C), stir after 10 minutes, add anthraquinone 4.0g(molecular weight 208,0.0195mol).After adding, be naturally warming up to room temperature, solution is glassy yellow.Add the hydrolysis of 200ml water, extract by ethyl acetate, solvent evaporated.Add acetic acid 300ml, KI and each 30g of inferior sodium phosphate, backflow.React 1 hour, cooling, cooling leaches, and obtains the faint yellow product of 2.8g.Boil 1 hour with the water/THF of 15/100, let cool and leach, repeated multiple times, obtain 7.7g faint yellow solid product, molecular weight 480, purity 95.0%, productive rate 78.48%.
Second step,
At the there-necked flask of a 1000ml; join mechanical stirring, Ar gas shielded, add the dichloro-intermediate 7.6g(molecular weight 480 that the first step generates; 0.015mol); 4-biphenylboronic acid Knit-the-brows alcohol ester 9.24g(molecular weight 280,0.033mol), catalyst P d (PPh3) 4 consumption 1.8g(molecular weight 1154; 0.001556mol); aqueous sodium carbonate 120ml(2M), toluene 300ml, ethanol 150ml.Stirring and refluxing, with TLC monitoring reaction, reacts completely after coreaction 5hs.Cooling, separates, evaporate to dryness, uses column chromatography methods separated product, the ethyl acetate of eluent 1:1: sherwood oil, obtain 9.6g faint yellow solid compound 1.Molecular weight of product 716, purity 99.2%, productive rate: 88.64%.
The mass spectrometric detection data of gained compound 1 and Elemental analysis data refer to table 1.
Embodiment 2
The present embodiment prepares compound 2, and its structure is as follows:
This compounds composition three step is carried out, the first step,
Building-up process is same as embodiment 1 second step, just by raw material dichloro-intermediate 3-bromo-6-chlorine imidazo [1 wherein, 2-a] pyrimidine replacement, 4-biphenylboronic acid Knit-the-brows alcohol ester 4-bromobenzeneboronic acid Knit-the-brows alcohol ester makes raw material, all the other reagent do not become, react 1.5 hours, namely reaction completes, obtains faint yellow solid bromo-derivative intermediate.
Second step,
Building-up process is same as embodiment 1 the first step, just by a kind of raw material 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine 3-(4-bromophenyl wherein)-6-chlorine imidazo [1,2-a] pyrimidine replaces making raw material, all the other reagent do not become, and obtain faint yellow solid two chloromethylated intermediate.
3rd step,
Building-up process is same as embodiment 1 second step, just raw material 4-biphenylboronic acid Knit-the-brows alcohol ester phenylo boric acid Knit-the-brows alcohol ester is wherein replaced, and two chloromethylated intermediates, two chloromethylated intermediates that second step synthesizes here are replaced making raw material, all the other reagent do not become, and obtain compound as white solid 2.
The mass spectrometric detection data of gained compound 2 and Elemental analysis data refer to table 1.
Embodiment 3
The present embodiment prepares compound 3, and its structure is as follows:
This compounds composition three step is carried out, the first step,
Building-up process is same as embodiment 1 second step, just raw material 4-biphenylboronic acid Knit-the-brows alcohol ester phenylo boric acid Knit-the-brows alcohol ester is wherein replaced, and by two chloromethylated intermediates with 5,7-dichloro-imidazole also [1,2-a] pyrimidine replace make raw material, all the other reagent do not become, and react two hours, obtain micro-yellow solid monochlor(in)ate compound.
Second step,
Building-up process is same as embodiment 1 second step, just raw material 4-biphenylboronic acid Knit-the-brows alcohol ester is wherein replaced with 4-bromobenzeneboronic acid Knit-the-brows alcohol ester, and by two chloromethylated intermediates 7-phenyl-5-chlorine imidazo [1,2-a] pyrimidine replace make raw material, all the other reagent do not become, and obtain micro-yellow solid monochlor(in)ate compound.
3rd step,
Building-up process is same as embodiment 1 the first step, and just replaced making raw material by the monobromo intermediate that this experiment second step synthesizes of raw material 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine wherein, all the other reagent do not become, and obtain faint yellow solid compound 3.
The mass spectrometric detection data of gained compound 3 and Elemental analysis data refer to table 1.
Embodiment 4
The present embodiment prepares compound 4, and its structure is as follows:
Building-up process is same as embodiment 1 the first step, just the bromo-6-of a kind of raw material 3-chloro-imidazo [1,2-a] pyrimidine is wherein replaced making raw material with 2-(4-bromophenyl)-imidazo [1,2-a]-7-methylpyrimidine, all the other reagent do not become, and obtain faint yellow solid compound 4.
The mass spectrometric detection data of gained compound 4 and Elemental analysis data refer to table 1.
Embodiment 5
The present embodiment prepares compound 5, and its structure is as follows:
Building-up process is same as embodiment 1 the first step, just the bromo-6-of a kind of raw material 3-chloro-imidazo [1,2-a] pyrimidine is wherein replaced making raw material with 2-(3-bromophenyl)-imidazo [1,2-a]-7-methylpyrimidine, all the other reagent do not become, and obtain faint yellow solid compound 5.
The mass spectrometric detection data of gained compound 5 and Elemental analysis data refer to table 1.
Embodiment 6
The present embodiment prepares compound 6, and its structure is as follows:
Building-up process is same as embodiment 1 the first step, just by the bromo-6-of a kind of raw material 3-chloro-imidazo [1,2-a] pyrimidine wherein with 2-(4-bromophenyl)-7-trifluoromethyl imidazoles also [1,2-a] pyrimidine replace making raw material, all the other reagent do not become, and obtain faint yellow solid compound 6.
The mass spectrometric detection data of gained compound 6 and Elemental analysis data refer to table 1.
Embodiment 7
The present embodiment prepares compound 7, and its structure is as follows:
Building-up process is same as embodiment 1 the first step, just by the chloro-imidazo [1 of the bromo-6-of a kind of raw material 3-wherein, 2-a] pyrimidine 7-(4-bromophenyl)-5-(methylthio group) imidazo [1,2-c] pyrimidine replace make raw material, all the other reagent do not become, and obtain faint yellow solid compound 7.
The mass spectrometric detection data of gained compound 7 and Elemental analysis data refer to table 1.
Embodiment 8
The present embodiment prepares compound 8, and its structure is as follows:
Building-up process is same as embodiment 1 the first step, just by the chloro-imidazo [1 of the bromo-6-of a kind of raw material 3-wherein, 2-a] pyrimidine with 2-(p-methylphenyl)-6(to bromophenyl) imidazo [1,2-a] pyrimidine replace make raw material, all the other reagent do not become, and obtain faint yellow solid compound 8.
The mass spectrometric detection data of gained compound 8 and Elemental analysis data refer to table 1.
Embodiment 9
The present embodiment prepares compound 9, and its structure is as follows:
This compounds composition five step is carried out, the first step,
At the there-necked flask of a 500ml, join mechanical stirring, Ar gas shielded; add 3-bromo-6-chlorine imidazo [1; 2-a] pyrimidine 7.6g(molecular weight 231,0.033mol), phenylo boric acid Knit-the-brows alcohol ester 6.73g(molecular weight 204; 0.033mol); catalyst P d (PPh3) 4 consumption 1.8g(molecular weight 1154,0.001556mol), aqueous sodium carbonate 100ml(2M); toluene 150ml, ethanol 100ml.Stirring and refluxing, with TLC monitoring reaction, reacts completely after reaction 1.5hs.Cooling, separates, evaporate to dryness, uses column chromatography methods separated product, the ethyl acetate of eluent 1:1: sherwood oil, obtain the micro-yellow solid compound of 7.3g, purity 99.2%, productive rate: 95.64%.
Second step,
Building-up process is same as previous step, just by the chloro-imidazo [1 of the bromo-6-of raw material 3-wherein, 2-a] pyrimidine 3-phenyl-6-chlorine imidazo [1,2-c] pyrimidine replaces, 4-bromobenzeneboronic acid Knit-the-brows alcohol ester replaces phenylo boric acid Knit-the-brows alcohol ester to make raw material, all the other reagent do not become, and obtain faint yellow solid bromo-derivative.
3rd step,
At one 1000 milliliters of there-necked flasks, join mechanical stirring, Ar gas shielded, add the faint yellow bromo-derivative 8.4g(molecular weight 349 that previous step synthesizes, 0.024mol), the anhydrous THF of 100ml, be chilled to-78 DEG C, stir the lower BuLi(2.4M dripping 12ml, 0.0288mol), temperature maintains-78 DEG C always,-78 DEG C time, B (OiPr) the 3(molecular weight 188.07 of 12ml is dripped after stirring 10min, proportion 0.9574, 0.061mol), stir to room temperature (with 3hrs), add dilute acid hydrolysis, divide water-yielding stratum, be neutralized to neutrality, add sodium-chlor, remove the THF be dissolved in water under reduced pressure, adularescent solid is separated out, filter, obtain product 7.2g solid 4-(3-phenylimidazole also [1, 2-a] pyrimidine-6-base) phenylo boric acid, productive rate 95.5%.
4th step,
At the there-necked flask of a 1000ml, join mechanical stirring, Ar gas shielded; add 9; 10-dibromoanthracene 11.7g(molecular weight 334,0.035mol), 4-(1-naphthyl) phenylo boric acid 8.7g(molecular weight 248; 0.035mol); catalyst P d (PPh3) 4 consumption 1.8g(molecular weight 1154,0.001556mol), aqueous sodium carbonate 120ml (2M); toluene 250ml, ethanol 150ml.Stirring and refluxing, with TLC monitoring reaction, reacts completely after reaction 1.5hs.Cooling, separates, evaporate to dryness, uses column chromatography methods separated product, the ethyl acetate of eluent 1:5: sherwood oil, obtain 15.8g white solid 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1), molecular weight of product 458, purity 98.7%, productive rate: 97.5%.
5th step,
Building-up process is same as the present embodiment the 4th step, just by a kind of raw material 9 wherein, 10-dibromoanthracene 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1) replacement, 4-(1-naphthyl) phenylo boric acid 4-(3-phenylimidazole also [1,2-a] pyrimidine-6-base) phenylo boric acid replace make raw material, all the other reagent do not become, and obtain compound as white solid 9.
The mass spectrometric detection data of gained compound 9 and Elemental analysis data refer to table 1.
Embodiment 10
The present embodiment prepares compound 10, and its structure is as follows:
Synthetic route is as follows:
Building-up process divides work three step, the first step, be same as embodiment 9 the 4th step, just use 3-(4-bromophenyl)-6-chlorine imidazo [1,2-a] pyrimidine replaces 3-phenyl-6-(to bromophenyl) imidazo [1,2-a] pyrimidine makes starting raw material, obtains 4-(6-chlorine imidazo [1,2-a] pyrimidin-3-yl) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1) replacement, 4-(1-naphthyl) phenylo boric acid 4-(6-chlorine imidazo [1,2-a] pyrimidin-3-yl) phenylo boric acid replacement, all the other reagent do not become, and obtain corresponding chloro intermediate; 3rd step is same as embodiment 9 the 4th step, is just replaced by raw material 9, the 10-dibromoanthracene chloro intermediate that step is synthesized, 4-(1-naphthyl) phenylo boric acid phenylo boric acid Knit-the-brows alcohol ester replacement, all the other reagent do not become, and obtain compound as white solid 10.
The mass spectrometric detection data of gained compound 10 and Elemental analysis data refer to table 1.
Embodiment 11
The present embodiment prepares compound 11, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 5-(to bromophenyl)-7-phenylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-phenylimidazole also [1,2-a] pyrimidine-5-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1) replacement, 4-(1-naphthyl) phenylo boric acid 4-(7-phenylimidazole also [1,2-a] pyrimidine-5-base) phenylo boric acid replacement, obtain compound as white solid 11.
The mass spectrometric detection data of gained compound 11 and Elemental analysis data refer to table 1.
Embodiment 12
The present embodiment prepares compound 12, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 2-(to bromophenyl)-7-Methylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1) replacement, 4-(1-naphthyl) phenylo boric acid 4-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid replacement, obtain compound as white solid 12.
The mass spectrometric detection data of gained compound 12 and Elemental analysis data refer to table 1.
Embodiment 13
The present embodiment prepares compound 13, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by bromophenyl between starting raw material 2-()-7-Methylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 3-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1) replacement, 4-(1-naphthyl) phenylo boric acid 3-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid replacement, obtain compound as white solid 13.
The mass spectrometric detection data of gained compound 13 and Elemental analysis data refer to table 1.
Embodiment 14
The present embodiment prepares compound 14, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 3-(to bromophenyl)-7-trifluoromethyl imidazoles also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-trifluoromethyl imidazoles also [1,2-a] pyrimidin-3-yl) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1) replacement, 4-(1-naphthyl) phenylo boric acid 4-(7-trifluoromethyl imidazoles also [1,2-a] pyrimidin-3-yl) phenylo boric acid replacement, obtain compound as white solid 14.
The mass spectrometric detection data of gained compound 14 and Elemental analysis data refer to table 1.
Embodiment 15
The present embodiment prepares compound 15, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material with 2-p-methylphenyl-6-(to bromophenyl) imidazo [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(2-p-methylphenyl imidazo [1,2-a] pyrimidine-6-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 9-(4-(1-naphthyl) phenyl)-10-bromine anthracene (AN1) replacement, 4-(1-naphthyl) phenylo boric acid 4-(2-p-methylphenyl imidazo [1,2-a] pyrimidine-6-base) phenylo boric acid replacement, obtain compound as white solid 15.
The mass spectrometric detection data of gained compound 15 and Elemental analysis data refer to table 1.
Embodiment 16
The present embodiment prepares compound 16, and its structure is as follows:
Building-up process divides work two step, the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 10,10 '-two bromo-9,9 ' dianthranides replace, 4-(1-naphthyl) phenylo boric acid 4-(6-chlorine imidazo [1,2-a] pyrimidin-3-yl) phenylo boric acid replacement, all the other reagent do not become, and obtain corresponding dichloro-intermediate; Second step is same as embodiment 9 the 4th step, is just replaced by raw material 9, the 10-dibromoanthracene dichloro-intermediate synthesized here, 4-(1-naphthyl) replacement of phenylo boric acid phenylo boric acid Knit-the-brows alcohol ester, all the other reagent do not become, and obtain faint yellow solid compound 16.
The mass spectrometric detection data of gained compound 16 and Elemental analysis data refer to table 1.
Embodiment 17
The present embodiment prepares compound 17, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 5-(to bromophenyl)-7-phenylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-phenylimidazole also [1,2-a] pyrimidine-5-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(7-phenylimidazole also [1,2-a] pyrimidine-5-base) phenylo boric acid replacement, obtain faint yellow solid compound 17.
The mass spectrometric detection data of gained compound 17 and Elemental analysis data refer to table 1.
Embodiment 18
The present embodiment prepares compound 18, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 2-(to bromophenyl)-7-Methylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid replacement, obtain faint yellow solid compound 18.
The mass spectrometric detection data of gained compound 18 and Elemental analysis data refer to table 1.
Embodiment 19
The present embodiment prepares compound 19, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by bromophenyl between starting raw material 2-()-7-Methylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 3-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 3-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid replacement, obtain faint yellow solid compound 19.
The mass spectrometric detection data of gained compound 19 and Elemental analysis data refer to table 1.
Embodiment 20
The present embodiment prepares compound 20, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 2-(to bromophenyl)-7-trifluoromethyl imidazoles also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-trifluoromethyl imidazoles also [1,2-a] pyrimidine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(7-trifluoromethyl imidazoles also [1,2-a] pyrimidine-2-base) phenylo boric acid replacement, obtain faint yellow solid compound 20.
The mass spectrometric detection data of gained compound 20 and Elemental analysis data refer to table 1.
Embodiment 21
The present embodiment prepares compound 21, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 7-(to bromophenyl)-5-thiamazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(5-thiamazole also [1,2-a] pyrimidin-7-yl) phenylo boric acid; Second step is same as embodiment 9 the 4th step, is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(5-thiamazole also [1,2-a] pyrimidin-7-yl) phenylo boric acid replacement, obtain faint yellow solid compound 21.
The mass spectrometric detection data of gained compound 21 and Elemental analysis data refer to table 1.
Embodiment 22
The present embodiment prepares compound 22, and its structure is as follows:
Building-up process divides work two step, the first step is same as embodiment 9 the 3rd step, just starting raw material is used 2-(p-methylphenyl)-6-(is to bromophenyl) imidazo [1,2-a] pyrimidine replacement, all the other reagent do not become, obtain 4-(2-(p-methylphenyl) imidazo [1,2-a] pyrimidine-6-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(2-(p-methylphenyl) imidazo [1,2-a] pyrimidine-6-base) phenylo boric acid replacement, obtain faint yellow solid compound 22.
The mass spectrometric detection data of gained compound 22 and Elemental analysis data refer to table 1.
Embodiment 23
The present embodiment prepares compound 23, and its structure is as follows:
This compou nd synthesis process divides three steps to carry out, the first step,
At the there-necked flask of a 1000ml, join mechanical stirring, Ar gas shielded; add 10,10 '-two bromo-9,9 '-dianthranide (BA) 17.9g(molecular weight 512; 0.035mol); 2-naphthalene boronic acids 6.1g(molecular weight 172,0.035mol), catalyst P d (PPh3) 4 consumption 1.8g(molecular weight 1154; 0.001556mol); aqueous sodium carbonate 120ml(2M), toluene 300ml, ethanol 150ml.Stirring and refluxing, with TLC monitoring reaction, reacts completely after coreaction 1.5hs.Cooling, separates, evaporate to dryness, uses column chromatography methods separated product, the ethyl acetate of eluent 1:5: sherwood oil, obtain 18.93g white solid product.Molecular weight of product 558, purity 98.0%, productive rate: 95.0%.
Second step,
Second step is same as embodiment 9 the 3rd step, is to bromophenyl by starting raw material 3-() also [1,2-a] pyrimidine replacement of-6-phenylimidazole, all the other reagent do not become, and obtain 4-(6-phenylimidazole also [1,2-a] pyrimidin-3-yl) phenylo boric acid.
3rd step,
3rd step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 10-(2-naphthyl)-10 '-bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(6-phenylimidazole also [1,2-a] pyrimidin-3-yl) phenylo boric acid replacement, obtain pale white solid compound 23.
The mass spectrometric detection data of gained compound 23 and Elemental analysis data refer to table 1.
Embodiment 24
It is as follows that the present embodiment prepares its structure of compound 24:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 5-(to bromophenyl)-7-phenylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-phenylimidazole also [1,2-a] pyrimidine-5-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 10-(2-naphthyl)-10 '-bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(7-phenylimidazole also [1,2-a] pyrimidine-5-base) phenylo boric acid replacement, obtain pale white solid compound 24.
The mass spectrometric detection data of gained compound 24 and Elemental analysis data refer to table 1.
Embodiment 25
The present embodiment prepares compound 25, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by starting raw material 2-(to bromophenyl)-7-Methylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 4-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 10-(4-(2-naphthyl) phenyl)-10 '-bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid replacement, obtain pale white solid compound 25.
The mass spectrometric detection data of gained compound 25 and Elemental analysis data refer to table 1.
Embodiment 26
The present embodiment prepares compound 26, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 3rd step, just by bromophenyl between starting raw material 2-()-7-Methylimidazole also [1,2-a] pyrimidine replacement, all the other reagent do not become, and obtain 3-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 10-(4-(2-naphthyl) phenyl)-10 '-bromo-9,9 ' dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 3-(7-Methylimidazole also [1,2-a] pyrimidine-2-base) phenylo boric acid replacement, obtain pale white solid compound 26.
The mass spectrometric detection data of gained compound 26 and Elemental analysis data refer to table 1.
Embodiment 27
The present embodiment prepares compound 27, and its structure is as follows:
Synthetic route is as follows:
Building-up process divides work two step, and the first step is same as embodiment 1 the first step, and just replaced by a kind of raw material 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine 3-bromo-8-chlorine imidazo [1,2-A] pyrazine wherein, all the other reagent do not become, and obtain two chloromethylated intermediates; Second step is same as embodiment 9 the 4th step, is just replaced by two chloromethylated intermediates of raw material 9,10-dibromoanthracene with one-step synthesis, 4-(1-naphthyl) phenylo boric acid 4-(2-naphthyl) replacement of phenylo boric acid Knit-the-brows alcohol ester, obtain faint yellow solid compound 27.
The mass spectrometric detection data of gained compound 27 and Elemental analysis data refer to table 1.
Embodiment 28
The present embodiment prepares compound 28, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 3-bromine imidazo [1,2-A] pyrazine replaces, 4-(1-naphthyl) phenylo boric acid replaces with to bromobenzeneboronic acid Knit-the-brows alcohol ester, obtain 3-(to bromophenyl) imidazo [1,2-A] pyrazine; Second step is same as embodiment 1 the first step, is to bromophenyl by a kind of raw material 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine 3-(wherein) replacement of imidazo [1,2-A] pyrazine, all the other reagent do not become, and obtain faint yellow solid compound 28.
The mass spectrometric detection data of gained compound 28 and Elemental analysis data refer to table 1.
Embodiment 29
The present embodiment prepares compound 29, and its structure is as follows:
Building-up process divides work two step, and the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 2-bromine imidazo [1,2-A] pyrazine replaces, 4-(1-naphthyl) phenylo boric acid replaces with to bromobenzeneboronic acid Knit-the-brows alcohol ester, obtain 2-(to bromophenyl) imidazo [1,2-A] pyrazine; Second step is same as embodiment 1 the first step, is to bromophenyl by a kind of raw material 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine 2-(wherein) replacement of imidazo [1,2-A] pyrazine, all the other reagent do not become, and obtain faint yellow solid compound 29.
The mass spectrometric detection data of gained compound 29 and Elemental analysis data refer to table 1.
Embodiment 30
The present embodiment prepares compound 30, and its structure is as follows:
Building-up process divides work two step, the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 3-bromo-8-chlorine imidazo [1,2-A] pyrazine replacement, 4-(1-naphthyl) phenylo boric acid 9-(4-(1-naphthyl) phenyl) replacement of anthracene-10-boric acid Knit-the-brows alcohol ester, obtain a chloro thing intermediate; Second step embodiment 9 the 4th step, just raw material 9, the 10-dibromoanthracene chloro thing intermediate that step synthesizes is replaced, 4-(1-naphthyl) phenylo boric acid 4-(1-naphthyl) replacement of phenylo boric acid Knit-the-brows alcohol ester, all the other reagent do not become, and obtain micro-yellow solid compound 30.
The mass spectrometric detection data of gained compound 30 and Elemental analysis data refer to table 1.
Embodiment 31
The present embodiment prepares compound 31, and its structure is as follows:
Building-up process is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 2-(is to bromophenyl) imidazo [1,2-A] pyrazine replacement, 4-(1-naphthyl) phenylo boric acid 9-(4-(1-naphthyl) phenyl) replacement of anthracene-10-boric acid Knit-the-brows alcohol ester, all the other reagent do not become, and obtain compound as white solid 31.
The mass spectrometric detection data of gained compound 31 and Elemental analysis data refer to table 1.
Embodiment 32
The present embodiment prepares compound 32, and its structure is as follows:
Building-up process is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 3-(is to bromophenyl) imidazo [1,2-A] pyrazine replacement, 4-(1-naphthyl) phenylo boric acid 9-(4-(1-naphthyl) phenyl) replacement of anthracene-10-boric acid Knit-the-brows alcohol ester, all the other reagent do not become, and obtain compound as white solid 32.
The mass spectrometric detection data of gained compound 32 and Elemental analysis data refer to table 1.
Embodiment 33
The present embodiment prepares compound 33, and its structure is as follows:
Synthesis point three steps are carried out, the first step,
At the there-necked flask of a 2000ml, join mechanical stirring, Ar gas shielded.Add 3-bromo-8-chlorine imidazo [1,2-A] pyrazine 4.62g(molecular weight 231,0.02mol), connection pinacol borate 5.6g(molecular weight 254.2,0.022mol), Pd (dppf) Cl23.2g(0.0044mol), Potassium ethanoate 36g(molecular weight 138,0.26mol), Isosorbide-5-Nitrae dioxane 500ml.Start mechanical stirring, take a breath 3 times at reduced pressure conditions and keep Ar gas shielded afterwards, use TLC(thin-layer chromatography) monitoring reaction, to raw material completely dissolve, refluxes after 3 hours, reacts completely.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, obtains 5.04g product, productive rate 90.2%.
Second step,
Be same as embodiment 9 the 4th step, be by raw material 9,10-dibromoanthracene with 10,10 '-two bromo-9,9 '-dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 8-chlorine imidazo [1,2-A] pyrazine-3-boric acid Knit-the-brows alcohol ester replacement, obtain dichloro-thing intermediate;
3rd step
Be same as embodiment 9 the 4th step, just two chloromethylated intermediates of raw material 9,10-dibromoanthracene with second step synthesis here replaced, 4-(1-naphthyl) phenylo boric acid 4-biphenylboronic acid Knit-the-brows alcohol ester replacement, obtain faint yellow solid compound 33.
The mass spectrometric detection data of gained compound 33 and Elemental analysis data refer to table 1.
Embodiment 34
The present embodiment prepares compound 34, and its structure is as follows:
Building-up process divides work two step, the first step is same as embodiment 9 the 3rd step, just by raw material 3-phenyl-6-(to bromophenyl) imidazo [1,2-a] pyrimidine 3-(is to bromophenyl) imidazo [1,2-A] pyrazine replacement, all the other reagent do not become, and obtain 4-(imidazo [1,2-A] pyrazine-3-base) phenylo boric acid; Second step embodiment 9 the 4th step is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 '-dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(imidazo [1,2-A] pyrazine-3-base) phenylo boric acid replacement, all the other reagent do not become, and obtain micro-yellow solid compound 34.
The mass spectrometric detection data of gained compound 34 and Elemental analysis data refer to table 1.
Embodiment 35
The present embodiment prepares compound 35, and its structure is as follows:
Building-up process divides work two step, the first step is same as embodiment 9 the 3rd step, be to bromophenyl by raw material 3-phenyl-6-() imidazo [1,2-a] pyrimidine 2-(is to bromophenyl) imidazo [1,2-A] pyrazine replacement, all the other reagent do not become, and obtain 4-(imidazo [1,2-A] pyrazine-2-base) phenylo boric acid; Second step is same as embodiment 9 the 4th step, is with 10 by raw material 9,10-dibromoanthracene, 10 '-two bromo-9,9 '-dianthranide replaces, 4-(1-naphthyl) phenylo boric acid 4-(imidazo [1,2-A] pyrazine-2-base) phenylo boric acid replacement, all the other reagent do not become, and obtain micro-yellow solid compound 35.
The mass spectrometric detection data of gained compound 35 and Elemental analysis data refer to table 1.
Embodiment 36
The present embodiment prepares compound 36, and its structure is as follows:
Synthetic route is as follows:
Building-up process is divided into three steps, and the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 2-bromo anthraquinone replaces, 4-(1-naphthyl) phenylo boric acid 4-(6-chlorine imidazo [1,2-A] pyrimidin-3-yl) phenylo boric acid replacement, all the other reagent do not become, and obtain a chloromethylated intermediate; Second step is same as embodiment 9 the 4th step, is just replaced by raw material 9, the 10-dibromoanthracene chloromethylated intermediate that the first step is synthesized, 4-(1-naphthyl) phenylo boric acid phenylo boric acid Knit-the-brows alcohol ester replacement, all the other reagent do not become, and obtain anthraquinone derivative intermediate; 3rd step synthesis is same as embodiment 1 the first step, is just replaced by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 2-bromonaphthalene, and the anthraquinone anthraquinone derivative intermediate of second step synthesis here replaces, and all the other reagent do not become, and obtain micro-yellow solid compound 36.
The mass spectrometric detection data of gained compound 36 and Elemental analysis data refer to table 1.
Embodiment 37
The present embodiment prepares compound 37, and its structure is as follows:
Building-up process is divided into four steps, and the first step is same as embodiment 33 the first step, just by bromo-for raw material 3-8-chlorine imidazo [1,2-A] replacement of pyrazine 3-bromo-6-chlorine imidazo [1,2-A] pyrimidine, other reagent does not become, obtain 6-chlorine imidazo [1,2-A] pyrimidine-3-boric acid Knit-the-brows alcohol ester; Second step is same as embodiment 9 the 4th step, is just replaced by raw material 9,10-dibromoanthracene 2-bromo anthraquinone, 4-(1-naphthyl) phenylo boric acid 6-chlorine imidazo [1,2-A] replacement of pyrimidine-3-boric acid Knit-the-brows alcohol ester, all the other reagent do not become, and obtain anthraquinone derivative intermediate; 3rd step is same as embodiment 9 the 4th step, is just replaced by the anthraquinone derivative intermediate of raw material 9,10-dibromoanthracene with one-step synthesis, 4-(1-naphthyl) replacement of phenylo boric acid phenylo boric acid Knit-the-brows alcohol ester, all the other reagent do not become, and obtain new anthraquinone derivative intermediate; 4th step synthesis is same as embodiment 1 the first step, just replaced by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 2-bromonaphthalene, the anthraquinone new anthraquinone derivative intermediate of the 3rd step synthesis here replaces, all the other reagent do not become, and obtain micro-yellow solid compound 37.
The mass spectrometric detection data of gained compound 37 and Elemental analysis data refer to table 1.
Embodiment 38
The present embodiment prepares compound 38, and its structure is as follows:
Building-up process is divided into two steps, the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 2-bromo anthraquinone replaces, 4-(1-naphthyl) phenylo boric acid 4-(7-Methylimidazole also [1,2-A] pyrimidine-2-base) phenylo boric acid replacement, all the other reagent do not become, and obtain anthraquinone derivative intermediate; Second step synthesis is same as embodiment 1 the first step, is just replaced by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 2-bromonaphthalene, and the anthraquinone anthraquinone derivative intermediate of second step synthesis here replaces, and all the other reagent do not become, and obtain micro-yellow solid compound 38.
The mass spectrometric detection data of gained compound 38 and Elemental analysis data refer to table 1.
Embodiment 39
The present embodiment prepares compound 39, and its structure is as follows:
Building-up process is divided into two steps, the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 2-bromo anthraquinone replaces, 4-(1-naphthyl) phenylo boric acid 4-(3-phenylimidazole also [1,2-A] pyrazine-8-base) phenylo boric acid replacement, all the other reagent do not become, and obtain anthraquinone derivative intermediate; Second step synthesis is same as embodiment 1 the first step, is just replaced by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 2-bromonaphthalene, and the anthraquinone anthraquinone derivative intermediate of second step synthesis here replaces, and all the other reagent do not become, and obtain pale white solid compound 39.
The mass spectrometric detection data of gained compound 39 and Elemental analysis data refer to table 1.
Embodiment 40
The present embodiment prepares compound 40, and its structure is as follows:
Building-up process is divided into two steps, and the first step is same as embodiment 9 the 4th step, just by raw material 9,10-dibromoanthracene 2-bromo anthraquinone replaces, 4-(1-naphthyl) phenylo boric acid 4-(imidazo [1,2-A] pyrimidin-3-yl) phenylo boric acid replacement, all the other reagent do not become, and obtain anthraquinone derivative intermediate; Second step synthesis is same as embodiment 1 the first step, is just replaced by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 2-bromonaphthalene, and the anthraquinone anthraquinone derivative intermediate of second step synthesis here replaces, and all the other reagent do not become, and obtain pale white solid compound 40.
The mass spectrometric detection data of gained compound 40 and Elemental analysis data refer to table 1.
Below mass spectrum and the Elemental analysis data of compound 1 to compound 40 of the present invention:
The Application Example of each compound of the present invention
Conveniently compare the transmission performance of these electron transport materials, the present invention devises one simple
The structure of organic electroluminescence device is:
Substrate/anode/hole-injecting material (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode.
Substrate can use the substrate in conventional organic luminescence device, such as: glass or plastics.In organic electroluminescence device of the present invention makes, select glass substrate, ITO makes anode material.
Hole-injecting material adopts 2-TNATA.
Hole transmission layer can adopt various tri-arylamine group material.Hole mobile material selected in organic electroluminescence device of the present invention makes is NPB.
Luminescent layer adopts light emitting host material EM1 and luminescent dye TBPe to adulterate and is total to the mode of steaming, and wherein the doping ratio of TBPe is 5% of EM1.
Electron transfer layer uses efficent electronic transport material Bphen and material of the present invention, and wherein Bphen is as comparative material.
The structure of 2-TNATA, NPB, TPBe, Bphen and EM1 is respectively:
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., can be also electron injecting layer/metal-layer structure, as LiF/Al, Li 2the common cathode structures such as O/Al.Cathode material selected in organic electroluminescence device of the present invention makes is LiF/Al.
Embodiment 41
Compound in the present embodiment is as the electron transport material in organic electroluminescence device, and EML is as emitting layer material, and prepared multiple organic electroluminescence device altogether, its structure is:
ITO/2-TNATA (60nm)/NPB(40nm)/EM1 (30nm)/ETL material (20nm)/LiF(0.5nm)/Al(150nm);
In contrast organic electroluminescence device, electron transport material selects Bphen, and all the other organic electroluminescence devices select material of the present invention.
In the present embodiment, organic electroluminescence device preparation process is as follows:
Sheet glass supersound process in commercial detergent of ITO transparency conducting layer will be coated with, rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and remove moisture content completely, by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10 -5~ 9 × 10 -3pa, on above-mentioned anode tunic, vacuum evaporation 2-TNATA is as hole-injecting material, and evaporation rate is 0.1nm/s, and evaporation thickness is 60nm;
On hole injection layer, vacuum evaporation NPB is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
Mode evaporation EM1 and TBPe adopting double source to steam altogether on hole transmission layer is as the luminescent layer of device, and wherein the evaporation rate of EM1 is the evaporation rate of 0.1nm/s, TBPe is 0.005nm/s, and evaporation total film thickness is 30nm;
On luminescent layer, vacuum evaporation one deck compound 1,2,6,9,18,23,27,33,37 or Bphen are as the electron transfer layer of device, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
The upper vacuum evaporation thickness of electron transfer layer (ETL) be the LiF of 0.5nm as electron injecting layer, thickness is the negative electrode of Al layer as device of 150nm.
Organic electroluminescence device performance sees the following form:
Above result shows, new organic materials of the present invention is used for organic electroluminescence device, can effectively reduce landing voltage, and improving current efficiency, is electron transport material of good performance.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that, under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.

Claims (7)

1. an organic compound, is characterized in that, has the structure as shown in formula I:
Wherein:
A and B one of them be N, another be H in CH group or CH group by the alkyl of C1-12, carbonatoms be the aryl of 6-30, carbonatoms is the heterocyclic aryl ,-CF of 6-30 3,-SCH 3in a kind of group of replacement;
N value 1 or 2;
Ar is selected from anthryl, phenyl, xenyl, naphthyl, naphthylphenyl be the anthryl that replaces of a kind of group wherein, anthrylene, phenyl, xenyl, naphthyl, naphthylphenyl be the anthrylene that replaces of a kind of group wherein, dianthranide base, the dianthranide base of phenyl, xenyl, naphthyl, naphthylphenyl, sub-dianthranide base, phenyl, xenyl, naphthyl, naphthylphenyl wherein the sub-dianthranide base that replaces of a kind of group one of them;
L is bridge linkage group, be selected from singly-bound, three substituted heterocycle aryl, Sauerstoffatom, nitrogen-atoms or sulphur atom that sub-heterocyclic aryl that trisubstituted aryl that arylidene that carbonatoms is 6-30, carbonatoms are 6-30, carbonatoms are 6-30, carbonatoms are 6-30 one of them;
Ar 1and Ar 2separately be selected from H, phenyl, C 1-12alkyl ,-CF 3,-SCH 3, phenyl, xenyl, the naphthyl wherein phenyl that replaces of a kind of group, naphthyl, C 1-12alkyl ,-CF 3,-SCH 3, phenyl, xenyl, the naphthyl wherein naphthyl that replaces of a kind of group, five yuan or hexa-member heterocycle aryl, the aliphatic alkyl of 1-12 carbon atom one of them.
2. organic compound according to claim 1, is characterized in that, described compound has formula II or the structure described in (III):
。
3. organic compound according to claim 1 and 2, is characterized in that, described bridge linkage group L is selected from one of them of singly-bound, phenylene, biphenylene, naphthylidene, pyridylidene, Sauerstoffatom, nitrogen-atoms or sulphur atom.
4. organic compound according to claim 1 and 2, is characterized in that, described organic compound is selected from following structural formula:
5. the organic compound described in any one of claim 1-4, is applied in organic electroluminescence device.
6. a kind of organic compound being applied to organic electroluminescence device according to claim 5, is characterized in that, can be used as electron transport material.
7. an organic electroluminescence device, comprises substrate, and forms anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
The electron transport material of described electron transfer layer is one or more organic compound according to any one of claim 1-4.
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